Lithographic printing inks

ABSTRACT

A single fluid lithographic printing ink composition includes a hydrophobic phase and a hydrophilic fluid phase. The hydrophilic fluid phase contains water or a liquid polyol or both. The hydrophobic phase contains a hydrogen bonding vinyl polymer that can hydrogen bond with the hydrophilic fluid phase. The vinyl polymers are preferably branched, but remain soluble in the hydrophobic phase. The invention provides stable inks that can be used as single fluid inks with excellent fountain stability and resistance to toning.

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation-in-part of U.S. patentapplication Ser. No. 09/856,408 filed on May 3, 2001, which is anational stage of PCT/US99/28173 filed Nov. 29, 1999, which is acontinuation of U.S. patent application Ser. No. 09/201,411, filed onNov. 30, 1998, now U.S. Pat. No. 6,140,392, issued Oct. 31, 2000; andthis application is a continuation-in-part of provisional U.S. patentapplication Ser. No. 60/309,617 filed on Aug. 2, 2001, the disclosuresof each of which are incorporated herein by reference.

FIELD OF THE INVENTION

[0002] The present invention relates to compositions of lithographicprinting inks and lithographic printing methods.

BACKGROUND OF THE INVENTION

[0003] Printing inks generally include one or more vehicle polymers orresins and one or more colorants as principal components. Printing inkvehicles must meet a number of performance requirements that includeboth requirements related to the printing process, such as suitableconsistency and tack for sharp, clean images, suitable length to avoidfly or mist, or proper drying characteristics, and requirements relatedto the printed image, such as gloss, chemical resistance, durability, orcolor. In general, ink vehicles include one or more materials such asvegetable oils or fatty acids, resins, and polymers that contribute tothe end product properties, and may include other components such asorganic solvents, water, rheology modifiers, and so on that may affectbody, tack, or drying characteristics.

[0004] In lithographic printing, in particular, an inked printing platecontacts and transfers an inked image to a rubber blanket, and then theblanket contacts and transfers the image to the surface being printed.Lithographic plates are produced by treating the image areas of theplate with an oleophilic material and ensuring that the non-image areasare hydrophilic. In a typical lithographic printing process, the platecylinder first comes in contact with dampening rollers that transfer anaqueous fountain solution to the hydrophilic non-image areas of theplate. The dampened plate then contacts an inking roller, accepting theink only in the oleophilic image areas. The press operator mustcontinually monitor the printing process to insure that the correctbalance of the fountain solution and the ink is maintained so that theink adheres to the printing areas, but only the printing areas, of theplate in order to produce a sharp, well-defined print.

[0005] The industry has long sought an offset printing process andassociated materials that would not require a separate fountainsolution. Waterless plates have been made by applying to the non-imagearea a silicone rubber, which has a very low surface energy and is notwetted by the ink. The silicone-modified plates are expensive, however,and require expensive, specially-cooled press equipment because thefountain solution of the traditional two-fluid method also serves as acoolant. Other efforts have been directed to producing a single-fluidlithographic ink, i.e., an ink that does not require a separate fountainsolution, that can be used with the industry-standard presses andall-metal plates. Parkinson, in U.S. Pat. No. 4,045,232 (the entiredisclosure of which is expressly incorporated herein by reference)describes lithographic printing and earlier efforts directed toproducing a single-fluid lithographic ink and the tendency ofsingle-fluid inks to be unstable. Parkinson notes that ink emulsionscontaining a solution of glycerin and salts tend to “break,” with theresult that the glycerin wets the inking rollers preventing good inking.Parkinson suggests an improved single-fluid ink obtained by using anadditive that includes a resin treated with a concentrated mineral acid,and, optionally, a polyhydric or monohydric alcohol. Preferred polyolsare glycerin, ethylene glycol, and propylene glycol. DeSanto, Jr. et al,in U.S. Pat. No. 4,981,517 (the entire disclosure of which is expresslyincorporated herein by reference) describe a printing ink that is anemulsion of an oil-based phase and a water-miscible phase. The patenteesallege that an emulsion containing a significant portion of water (10%to 21%) and employing phosphoric acid as a critical component hasimproved stability against phase separation and can be used as asingle-fluid lithographic ink. The De Santo, Jr. composition furtherincludes as a diluent and emulsion stabilizer an oil with the propertiesof No. 1 and No. 2 fuel oils and a polyol emulsifier, of which glycerinand ethylene glycol are the only examples provided.

[0006] Nonetheless, due to various drawbacks of the single-fluidlithographic inks that have previously been proposed, including thelimited stability and poor definition and toning already mentioned, theindustry standard continues to be a dual-fluid lithographic ink thatincludes an ink component and a separate fountain solution component.

SUMMARY OF THE INVENTION

[0007] The invention provides a single fluid lithographic printing inkcomposition that includes a hydrophobic phase and an emulsifiedhydrophilic fluid phase. The hydrophobic phase comprises a hydrogenbonding vinyl resin. The terms “vinyl resin” and “vinyl polymer” areused synonymously in describing the invention and refer to polymersprepared by chain reaction polymerization, or addition polymerization,through carbon-carbon double bonds, using vinyl monomers (such asacrylic and methacrylic monomers, other vinyl monomers including vinylesters and vinyl aromatic monomers including styrene) and otherethylenically unsaturated monomers copolymerizable with these. The term“hydrogen bonding” vinyl polymers refers to those vinyl polymers havinggroups that form hydrogen bonds with the emulsified hydrophilic fluidphase.

[0008] The vinyl polymers of the invention are preferably branched byincluding in the polymerization reaction monomers that have two or more,preferably two reaction sites or by reacting the polymer with a limitedamount of crosslinker during or after polymerization. The “branched”vinyl polymer is one that remains usefully soluble in organic solvents,rather than a polymer that is crosslinked into an insoluble,three-dimensional network structure that can only be swelled bysolvents. The branched vinyl polymers of the invention unexpectedlyretain solubility in spite of significant branching.

[0009] The invention further provides a method of making an inkcomposition having a hydrophilic fluid phase and a hydrophobic phasethat includes an organic solution of vinyl resin that can form hydrogenbond interactions with the hydrophilic fluid phase. In another aspect ofthe invention, the hydrophobic phase includes one or more otheradditional resins or polymers.

[0010] The invention also provides a process of printing using thelithographic single fluid ink of the invention. The invention hasunexpectedly provided stable inks that can be used as single fluid inkswith excellent fountain stability and resistance to toning.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Lithographic ink compositions according to the invention aresingle-fluid inks having a hydrophobic continuous phase that contains ahydrogen bonding vinyl polymer and an emulsified phase that containswater, a liquid polyol, or both water and a liquid polyol. Thehydrophobic phase may contain further polymers and/or resins suitablefor ink vehicles as well as pigments, while the hydrophilic fluid phasemay contain additional materials as well as additives such as weak acidsor weak bases to enhance the hydrogen bonding strength of the fluid. Thelithographic ink compositions have a sufficient amount of hydrogenbonding between the hydrophobic phase and the hydrophilic phase so thatthe single fluid ink does not separate in the fountain and asufficiently limited amount of hydrogen bonding between the hydrophobicphase and the hydrophilic phase so that during application of the inkthe emulsion breaks and the water and/or polyol comes to the surface,wetting out the areas of the plate that are not to receive ink. Inksthat are stable in the fountain but break quickly to separate on theplate print cleanly without toning and provide consistent transfercharacteristics. Proper stability also may depend upon the particularhydrogen bonding vinyl polymer and the particular polyol chosen. Thecontent of hydrogen bonding groups and molecular weight of the polymerand the amount of the hydrogen bonding vinyl polymer in the ink may beadjusted to provide the desired stability. In general, it is believedthat an increase in hydrogen bonding groups on the vinyl resin should beaccompanied by a decrease in the amount of such resin included in thehydrophobic phase.

[0012] The hydrophilic fluid phase includes water, one or more liquidpolyols, or both water and one or more liquid polyols. A liquid polyolis an organic liquid with at least two hydroxyl groups. Polyethyleneglycol oligomers such as diethylene glycol, triethylene glycol, andtetraethylene glycol, as well as ethylene glycol, propylene glycol,1,3-propanediol, dipropylene glycol, 1,4-butanediol, and glycerol areexamples of liquid polyols that are preferred for the hydrophilic fluidphase of the single-fluid ink of the invention. The emulsified phasemay, of course, include mixtures of different liquid polyols or amixture water and one or more liquid polyols. In general, highermolecular weight liquid polyols may be preferred when the vinyl polymerof the hydrophobic phase has a higher equivalent weight with respect tothe hydrogen bonding groups.

[0013] The emulsified phase may include further materials. In oneembodiment, the emulsified phase may also include one or more solidpolyols. The solid polyols may be selected from solid polyol compoundsand solid polyol oligomers. Examples include, without limitation,2,3-butanediol, 1,6-hexanediol and other hexanediols, pentaerythritol,dipentaerythritol, hyclroxyl hyperbranched dendrimers,trimethylolethane, trimethylolpropane, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, andhydrogenated bisphenol A. Compounds having one hydroxyl group and up toabout 18 carbon atoms, preferably up to about 8 carbon atoms may also beincluded, such as cyclohexanol and stearyl alcohol. The emulsified phasemay also include a weak acid such as citric acid, tartaric acid, ortannic acid, or a weak base such as triethanolamine, which may beincluded in an amount of from about 0.01 weight percent up to about 2weight percent of the ink composition. Certain salts such as magnesiumnitrate may be included in amounts of from about 0.01 weight percent toabout 0.5 weight percent, preferably from about 0.08 to about 1.5 weightpercent, based on the weight of the ink composition, to help protect theplate and extend the life of the plate. A water soluble polymer, such aspoly(vinyl pyrrolidone), poly(vinyl alcohol), and poly(ethylene glycol),may be added to the emulsified. From about 0.5 weight percent to about1.5 weight percent of the water soluble polymer is included, based onthe weight of the ink composition.

[0014] Lithographic, single-fluid inks may be formulated with from about5% up to about 50%, preferably from about 10% to about 35%, andparticularly preferably from about 20% to about 30% of the emulsifiedfluid phase by weight based on the total weight of the ink composition.Unless another means for cooling is provided, there is preferably asufficient amount of emulsified fluid in the ink composition to keep theplate at a workably cool temperature, preferably at least about 5% byweight, more preferably at least about 10% by weight, and even morepreferably at least about 15% by weight, and up to about 50% by weight,preferably up to about 35% by weight, and more preferably up to about30% by weight. The amount of the emulsified fluid phase necessary toachieve good printing results without toning may depend upon the kind ofplate being used and may be determined by straightforward testing.

[0015] The vinyl polymer-containing continuous phase stabilizes theemulsified fluid phase. The stability is such that the two phases do notseparate in the fountain. During application of the ink, however, theemulsion breaks and the polyol comes to the surface, wetting out theareas of the plate that are not to receive ink. Inks that are stable inthe fountain but break quickly to separate on the plate print cleanlywithout toning and provide consistent transfer characteristics. Properstability also may depend upon the particular hydrogen-bonding vinylpolymer and the particular components of the emulsified phase chosen.The hydrogen bonding equivalent weight and molecular weight of the vinylpolymer, as well as the concentration of the vinyl polymer in thecontinuous phase, may be adjusted to provide the desired stability.Vinyl polymers with higher levels of hydrogen bonding groups (lowerequivalent weights) can generally be used in lower amounts, but ingeneral the concentration of hydrogen bonding groups may not beexcessively high or else the vinyl polymer will not be sufficientlysoluble in the continuous phase. Destabilizing interactions, such asbetween an additional polymer, resin, or other material of thecontinuous phase and the emulsified fluid phase, is avoided. In general,additional materials that are more hydrophilic than the hydrogen-bondingvinyl polymer are avoided.

[0016] The hydrophobic phase of the single-fluid ink includes at least avinyl polymer having groups that can hydrogen bond with one or morecomponents of the hydrophilic fluid phase. The hydrogen bonding vinylpolymers of the invention are prepared by polymerization of a monomermixture that includes one or more monomers that contain hydrogen bondinggroups or by adducting the polymer with hydrogen bonding groups orconverting other groups to the desired hydrogen bonding groups afterpolymerization. The vinyl polymers of the invention are advantageouslybranched by including in the polymerization reaction monomers that havetwo reaction sites or by reacting the polymer with a material having aplurality of groups reactive with the polymer. When the vinyl polymer isbranched, it nonetheless remains usefully soluble. By “soluble” it ismeant that the polymer can be diluted with one or more solvents. (Bycontrast, polymers may be crosslinked into gels, which are insoluble,three-dimensional network structures that are only be swelled bysolvents.) The branched vinyl resins of the invention unexpectedlyretain solvent dilutability in spite of significant branching.

[0017] The hydrogen bonding vinyl polymers of the invention may beprepared by polymerizing a monomer mixture that includes at least onemonomer that contains a hydrogen bonding group or a group that can beconverted to or adducted with a hydrogen bonding group afterpolymerization. Among preferred hydrogen bonding groups are carboxylicacid groups, carboxylic anhydride groups, primary amines or amineshaving alkyl substituents of three or fewer carbon atoms on the nitrogenatom, primary amides or amides having alkyl substituents of three orfewer carbons on the nitrogen atom, esters having pendant alkyl groupsof three or fewer carbon atoms, β-hydroxyl esters, hydroxyls, orsulfur-containing groups.

[0018] Carboxyl-functional vinyl polymers of the invention may beprepared by polymerization of a monomer mixture that includes at leastone acid-functional monomer or at least one monomer that has a groupthat is converted to an acid group following polymerization, such as ananhydride group. Examples of acid-functional or anhydride-functionalmonomers include, without limitation, α,β-ethylenically unsaturatedmonocarboxylic acids containing 3 to 5 carbon atoms such as acrylic,methacrylic, and crotonic acids; α,β-ethylenically unsaturateddicarboxylic acids containing 4 to 6 carbon atoms and the anhydrides andmonoesters those acids, such as maleic anhydride, maleic acid monomethylester, and fumaric acid; and acid-functional derivatives ofcopolymerizable monomers, such as the hydroxyethyl acrylate half-esterof succinic acid. Acid functionality may also be provided by other knownmeans, such as by reaction of an hydroxyl group with an anhydride or byhydrolysis of an ester, such as by hydrolysis of a tert-butylmethacrylate monomer unit. It is preferred to include an acid-functionalmonomer such as acrylic acid, methacrylic acid, or crotonic acid, or ananhydride monomer such as maleic anhydride or itaconic anhydride thatmay be hydrated after polymerization to generate acid groups. It ispreferred for the acid-functional vinyl polymer to have an acid numberof at least about 3 mg KOH per gram nonvolatile, preferably an acidnumber of from about 6 to about 30 mg KOH per gram nonvolatile, and morepreferably an acid number of from about 8 to about 25 mg KOH per gramnonvolatile, based upon the nonvolatile weight of the vinyl polymer.

[0019] Examples of amines and amide groups include, without limitation,primary amides, N-alkylamides in which the N-alkyl group has three orfewer carbon atoms, N,N′-dialkylamides in which each N-alkyl group hasthree or fewer carbon atoms, primary amines, N-alkylamines in which theN-alkyl group has three or fewer carbon atoms, N,N′-dialkylamines inwhich the N-alkyl group has three or fewer carbon atoms, phosphonamides,and sulfonamides. Examples of suitable amine and amide functional,ethylenically unsaturated monomers include, without limitation,acrylamide, methacrylamide, p-dimethylaminostyrene, N-,dimethylaminoethyl methacrylate, aminopropyl methacrylate, aminoethylacrylate, amninopropyl acrylate, aminoethyl methacrylate,1-vinyl-2-pyrrolidinone, N-alkylacrylamides, N-alkylmethacrylamides,N,N′-dialkylacrylamides, and N,N′-dialkylmethacrylamides, in which thealkyl group have 3 or fewer carbon atoms. Specific examples includeN-methylacrylamide, N-methylmethacrylamide, N-isopropyl acrylamide,N-isopropyl methacrylamide, N,N-dimethylacrylamide,N,N′-dimethylmethacrylamide, N,N′-diisopropylmethacrylamide, N-vinylformamide, and combinations of these.

[0020] Examples of sulfur-containing groups include sulfonic acids,sulfonamides, sulfoxides, sulfones, and mercaptans. Mercaptans may beincluded as chain transfer agents. Examples of suitable monomersinclude, without limitation, 2-acrylamido-2-methylpropane sulfonic acid,methyl vinyl sulfone, methyl vinyl sulfoxide, and sodium vinylsulfonate. A copolymer of sodium vinyl sulfonate may be acidified, thentreated with dialkylamine to give the sulfonamide.

[0021] Examples of monomers providing phosphorous-containing groupsinclude, without limitation, vinyl phosphoric acid, which may beesterified to give the phosphate or amidified with dialkylamine to givethe phosphonamide.

[0022] Examples of suitable ethylenically unsaturated hydroxyl monomersinclude, without limitation, hydroxyethyl acrylate, hydroxypropylacrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate,hydroxypropyl methacrylate, and hydroxybutyl methacrylate.Hydroxyl-functional groups may also be obtained on the vinyl polymer,for example, by hydrolysis of ester groups, e.g. hydrolysis of vinylacetate monomer units to vinyl alcohol, or by reaction of an acid groupwith an oxirane group, e.g. reaction of a glycidyl methacrylate monomerunit with acetic acid or reaction of a methacrylic acid monomer unitwith ethylene oxide. It is preferred to add weakly basic materials tothe hydrophilic fluid phase in order to strengthen the hydrogen bondingbetween the hydroxyl-functional vinyl polymer and the components of thehydrophilic fluid phase.

[0023] Suitable esters include methyl, ethyl, n-propyl, and isopropylesters of polymerizable acids, for example methyl methacrilate, ethylacrylate, monomethyl maleate, diethyl maleate, and so on, as well asethylenically unsaturated esters of saturated acids having up to fourcarbon atoms such as the formate, acetate, propionates, and butyrates ofhydroxyethyl acrylate or hydroxyethyl methacrylate or vinyl formate,vinyl acetate, vinyl propionates, and vinyl butyrates.

[0024] Acetoacetate groups are also useful for hydrogen bonding andmonomers containing the acetoacetate group may be obtained by reactingan allyl halide with 2,4-pentanedione that has been treated with astrong base (e.g., KOH) to produce the stabilized carbanion. Theresulting acetoacetate-functional monomer is copolymerized to provide anacetoacetate-functional vinyl polymer. Another acetoacetate-functionalmonomer is acetoacetoxyethyl methacrylate.

[0025] The hydrogen bonding vinyl polymer of the invention may alsocontain a combination of the above functional groups capable of forminghydrogen bonding interactions. The vinyl polymers preferably has anequivalent weight, based on the hydrogen bonding groups, of preferablyat least about 1800 g/equivalent, more preferably at least about 2200g/equivalent, and preferably up to about 20,000 g/equivalent, morepreferably up to about 7200 g/equivalent.

[0026] The hydrogen bonding group of the vinyl polymer may be a hydrogendonating species and/or a hydrogen accepting species. It will beappreciated that the vinyl polymer and the hydrophilic fluid may havethe same chemical functional group participating as both the donorspecies and the acceptor species of the hydrogen bond pair. For example,hydroxyl groups on the vinyl polymer may interact with hydroxyl groupsof the hydrophilic phase. By the same token, the donor and acceptorspecies may be different chemical groups. For example, an amide groupmay hydrogen bond with an hydroxyl group. In addition, some functionalgroups on the hydrogen bonding vinyl polymers may serve as acceptorspecies, others as donor species, and others as both. In general, thewater and/or polyol(s) of the hydrophilic fluid phase can act both asacceptors and donors.

[0027] The strength of a hydrogen bond is related to the relativeacidity and basicity of the donor and acceptor species. If it is desiredto strengthen the hydrogen bond formed between a donor with a weaklyacidic hydrogen atom and an acceptor, it is possible to add acidicmaterials to the donor species to increase its hydrogen bondingaffinity. Alternatively, a weakly basic material may be added to ahydrogen acceptor to increase the strength of a hydrogen bond. In somesituations, ionic interaction may be moderated and controlled byappropriate additions of weak acids and weak basis to the donor andacceptors.

[0028] The hydrogen bonding vinyl polymers are branched. In oneembodiment, the hydrogen bonding vinyl polymers are significantlybranched. The vinyl polymer that is branched but usefully soluble. Thebranched vinyl polymers of the invention is diluted, rather than swollenor dispersed, by addition of solvent. The branching may be accomplishedby a number of methods. In a first method, a monomer with two or morepolymerizable double bonds is included in the polymerization reaction.In a second method, a pair of ethylenically unsaturated monomers, eachof which has in addition to the polymerizable double bond at least oneadditional functionality reactive with the additional functionality onthe other monomer, are included in the monomer mixture beingpolymerized. A third method consists of crosslinking the polymer with acrosslinker having at least two functional groups that react withfunctional groups on the polymer.

[0029] Preferably, the vinyl resin of the invention is polymerized usingat least one monomer having two or more polymerizable ethylenicallyunsaturated bonds. Illustrative examples of monomers having two or moreethylenically unsaturated moieties include, without limitation,(meth)acrylate esters of polyols such as 1,4-butanedioldi(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycoldi(meth)acrylate, trimethylolpropane tri(meth)acrylate,tetramethylolmethane tetra(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol penta(meth)acrylate,dipentaerythritol hexa(meth)acrylate, alkylene glycol di(meth)acrylatesand polyalkylene glycol di(meth)acrylates, such as ethylene glycoldi(meth)acrylate, butylene glycol di(meth)acrylate, diethylene glycoldi(meth)acrylate, triethylene glycol di(meth)acrylate, and polyethyleneglycol di(meth)acrylate; divinylbenzene, allyl methacrylate, diallylphthalate, diallyl terephthalate, and the like, singly or incombinations of two or more. Of these, divinylbenzene, butylene glycoldimethacrylate, butanediol dimethacrylate, trimethylolpropanetriacrylate, and pentaerythritol tetra-acrylate are highly preferred,and divinylbenzene is still more highly preferred.

[0030] Preferably, the branched vinyl polymer is polymerized using atleast about 0.008 equivalents per 100 grams of monomer polymerized of atleast one monomer having at least two ethylenically unsaturatedpolymerizable bonds, or 0.004 equivalents per 100 grams of monomerpolymerized of each of two monomers having mutually reactive groups inaddition to an ethylenically unsaturated polymerizable bond. Preferably,the branched vinyl polymer is polymerized using from about 0.012 toabout 0.08 equivalents, and more preferably from about 0.016 to about0.064 equivalents per 100 grams of monomer polymerized of thepolyfunctional monomer or monomers having at least two ethylenicallyunsaturated polymerizable bonds or of the pair of monomers having onepolymerization bond and one additional mutually reactive group. Thepolyfunctional monomer or monomers preferably have from two to fourethylenically unsaturated polymerizable bonds, and more preferably twoethylenically unsaturated polymerizable bonds. In one embodiment it ispreferred for the branched vinyl resin to be prepared by polymerizing amixture of monomers that includes from about 0.5% to about 6%, morepreferably from about 1.2% to about 6%, yet more preferably from about1.2% to about 4%, and even more preferably from about 1.5% to about3.25% divinylbenzene based on the total weight of the monomerspolymerized. Commercial grades of divinylbenzene include mono-functionaland/or non-functional material. The amount of the commercial materialneeded to provide the indicated percentages must be calculated. Forexample, 5% by weight of a material that is 80% by weightdivinylbenzene/20% mono-functional monomers would provide 4% by weightof the divinylbenzene fraction.

[0031] The optimum amount of divinylbenzene or other monomer having atleast two polymerizable ethylenically unsaturated bond that is includedin the polymerization mixture depends to some extent upon the particularreaction conditions, such as the rate of addition of monomers duringpolymerization, the solvency of the polymer being formed in the reactionmedium chosen, the amount of monomers relative to the reaction medium,the half-life of the initiator chosen at the reaction temperature andthe amount of initiator by weight of the monomers, and may be determinedby straightforward testing.

[0032] Alternatively, the polymers can be crosslinked by including inthe monomer mixture at least a pair of monomers having at least onefunctionality reactive with the functionality of the other monomer.Preferably, the reaction of the additional functional groups takes placeduring the polymerization reaction, although this is not seen ascritical in the formation of a polymer according to the invention andthe reaction of the additional functional groups may be carried outpartially or wholly before or after polymerization. A variety of suchpairs of mutually reactive groups is possible. Illustrative examples ofsuch pairs of reactive groups include, without limitation, epoxide andcarboxyl groups, amine and carboxyl groups, epoxide and amine groups,epoxide and anhydride groups, amine and anhydride groups, hydroxyl andcarboxyl or anhydride groups, amine and acid chloride groups, alkyleneimine and carboxyl groups, organoalkoxysilane and carboxyl groups,isocyanate and hydroxyl groups, cyclic carbonate and amine groups,isocyanate and amine groups, and so on. When the hydrogen bonding groupsare included as one of the reactive groups, they are used in asufficient excess to provide the desired hydrogen bonding functionalityin the vinyl resin. Specific examples of such monomers include, withoutlimitation, glycidyl (meth)acrylate with (meth)acrylic acid,N-alkoxymethylated acrylamides (which react with themselves) such asN-isobutoxymethylated acrylamide, gamma methacryloxytrialkoxysilane(which reacts with itself), and combinations thereof. In connection withthe description of this invention, the term “(meth)acrylate” will beused to refer to both the acrylate and the methacrylate esters, the term“(meth)acrylic” will be used to refer to both the acrylic and themethacrylic compounds, and so on.

[0033] The polymers of the invention may also be branched by subjectingthe polymer to reaction with a limited amount of a crosslinking compoundafter polymerization. The amount of crosslinking is limited so that thevinyl polymer remains soluble in the continuous phase. Such crosslinkersinclude at least two functional groups reactive with functional groupson the polymer. The reactive groups on the crosslinker may be the sameor different, and the crosslinker will be selected according to whatfunctional groups are present on the polymer. It should be noted thatmany of the hydrogen bonding functional groups on the hydrogen bondingvinyl polymer are capable of being crosslinked. Generally, suchcrosslinking occurs at a low stoichiometric ratio so that after suchcrosslinking there are still available hydrogen bonding groups to formhydrogen bonds with components of hydrophilic fluid phase as describedabove. Examples of crosslinkers include, without limitation,polycarboxylic acids, polyamines, polyisocyanates, and polyhydroxylcontaining species. Non-limiting examples of crosslinkers includediethylene glycol, triethylene glycol, hexanediamine, adipic acid,neopentyl glycol, dipropylene glycol, tripropylene glycol,1,4-cyclohexanedimethanol, 1,6-hexanediol, 1,3-butanediol, hydrogenatedbisphenol A, 2,2,4-trimethyl-1,3-pentanediol, and the like.

[0034] Aluminum gellants may also be used as the external crosslinker.Such aluminum gellants may be aluminum salts, aluminum organiccomplexes, or aluminum alkoxides. The aluminum gellants crosslink thehydrogen bonding vinyl polymer by forming aluminum alkoxide bridgesbetween reactive groups on the polymer. Specific examples of aluminumgellants useful in the invention include, without limitation, aluminumacetoacetonate, aluminum triisopropoxide, aluminum tris-sec-butoxide,aluminum diisopropoxide aceto ester, aluminum oxyacylate (OAO fromChattem Chemicals), and combinations of these. In addition, alkoxylatedtitanates and zirconates may be used, for example, without limitation,di(cumyl)phenyl oxoethylene titanate, di(dioctyl) phosphato ethylenetitanate, diisopropyl distearoyl titanate, the corresponding zirconates,and combinations of these. Combinations of aluminum gellants,alkoxylated titanates, and alkoxylated zirconates are also useful.

[0035] Other monomers that may be polymerized along with the monomerscontaining hydrogen bonding groups include, without limitation, higheresters of α,β-ethylenically unsaturated monocarboxylic acids containing3 to 5 carbon atoms such as butanol and higher alcohol esters ofacrylic, methacrylic and crotonic acids; butanol and higher diesters ofα,β-ethylenically unsaturated dicarboxylic acids containing 4 to 6carbons; butyrate and higher vinyl esters, vinyl ethers, vinyl ketonessuch as vinyl ethyl ketone, and aromatic or heterocyclic aliphatic vinylcompounds.

[0036] Representative examples of suitable esters of acrylic,methacrylic, and crotonic acids include, without limitation, thoseesters from reaction with saturated aliphatic and cycloaliphaticalcohols containing 4 to 20 carbon atoms, such as for example n-butyl,isobutyl, tert-butyl, 2-ethylhexyl, lauryl, stearyl, cyclohexyl,trimethylcyclohexyl, tetrahydrofurfuryl, stearyl, sulfoethyl, andisobornyl acrylates, methacrylates, and crotonates; and polyalkyleneglycol acrylates and methacrylates. Representative examples of otherethylenically unsaturated polymerizable monomers include, withoutlimitation, such compounds as diesters of fumaric, maleic, and itaconicacid with alcohols such as butanol, isobutanol, and tert-butanol.Representative examples of aromatic or heterocyclic aliphatic vinylcompounds include, without limitation, such compounds as styrene,α-methyl styrene, vinyl toluene, tert-butyl styrene, and so on. Theselection of monomers is made on the basis of various factors commonlyconsidered in making ink varnishes, including the desired glasstransition temperature and the desired dilutability of the resultingpolymer in the solvent or solvent system of the ink composition.

[0037] The preferred vinyl polymers may be prepared by usingconventional techniques, preferably free radical polymerization in asemi-batch process. For instance, the monomers, initiator(s), and anychain transfer agent may be fed at a controlled rate into a suitableheated reactor charged with solvent in a semi-batch process.

[0038] Typical free radical sources are organic peroxides, includingdialkyl peroxides, such as di-tert-butyl peroxide and dicumyl peroxide,peroxyesters, such as tert-butyl peroxy 2-ethylhexanoate and tert-butylperoxy pivalate; peroxy carbonates and peroxydicarbonates, such astert-butyl peroxy isopropyl carbonate, di-2-ethylhexyl peroxydicarbonateand dicyclohexyl peroxydicarbonate; diacyl peroxides, such as dibenzoylperoxide and dilauroyl peroxide; hydroperoxides, such as cumenehydroperoxide and tert-butyl hydroperoxide; ketone peroxides, such ascyclohexanone peroxide and methylisobutyl ketone peroxide; andperoxyketals, such as 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane and 1,1-bis(tert-butyl peroxy)cyclohexane; as well as azo compounds such as2,2′-azobis(2-methylbutanenitrile), 2,2′-azobis(2-methyl)propionitrile,and 1,1′-azobis(cyclohexanecarbonitrile). Organic peroxides arepreferred. Particularly preferred is tert-butyl peroxy isopropylcarbonate The particular initiator and amount of initiator used dependsupon factors known to the person skilled in the art, such as thereaction temperature, the amount and type of solvent (in the case of asolution polymerization), the half-life of the initiator, and so on.

[0039] Chain transfer agents may also be used in the polymerization.Typical chain transfer agents are mercaptans such as octyl mercaptan, n-or tert-dodecyl mercaptan, thiosalicylic acid, mercaptocarboxylic acidssuch as mercaptoacetic acid and mercaptopropionic acid and their esters,and mercaptoethanol; halogenated compounds; and dimeric alpha-methylstyrene. Preferably, no chain transfer agent is included because of odorand other known drawbacks.

[0040] The addition polymerization such as by free radicalpolymerization is usually carried out in solution at temperatures fromabout 20° C. to about 300° C., preferably from about 150° C. to about200° C., more preferably from about 160° C. to about 165° C. Preferably,the polymerization is carried out with approximately the same reactiontemperature and using the same initiator(s) throughout. The initiatorshould be chosen so its half-life at the reaction temperature ispreferably no more than about thirty minutes, particularly preferably nomore than about five minutes, and yet more preferably no more than abouttwo minutes. Particularly preferred are initiators having a half-life ofless than about one minute at a temperature of from about 150° C. toabout 200° C. In general, more of the branching monomer can be includedwhen the initiator half-life is shorter and/or when more initiator isused. The vinyl polymer vehicles of the invention preferably have littleor no residual (unreacted) monomer content. In particular, the vinylvehicles are preferably substantially free of residual monomer, i.e.,have less than about 0.5% residual monomer, and even more preferablyless than about 0.1% residual monomer by weight, based on the totalweight of the monomers being polymerized.

[0041] In a semi-batch process, the monomer and initiator are added tothe polymerization reactor over a period of time, preferably at aconstant rate. Typically, the add times are from about 1 to about 10hours and add times of from about three to about five hours are common.Longer add times typically produce lower number average molecularweights. Lower number average molecular weights may also be produced byincreasing the ratio of solvent to monomer or by using a strongersolvent for the resulting polymer.

[0042] In general, the branched vinyl polymer of the invention has a lownumber average molecular weight and a broad polydispersity. The numberaverage molecular weight Mn and weight average molecular weight M_(w) ofa vinyl resin according to the invention can be determined by gelpermeation chromatography using polystyrene standards, which areavailable for up to 6 million weight average molecular weight, accordingto well-accepted methods. Polydispersity is defined as the ratio ofM_(w) /M_(n). In one embodiment, the vinyl polymer has a number averagemolecular weight of at least about 1000, and more preferably at leastabout 2000. The number average molecular weight is also preferably lessthan about 15,000, more preferably less than about 10,000, and even morepreferably less than about 8500. A preferred range for M_(n) is fromabout 1000 to about 10,000, a more preferred range for M_(n) is fromabout 2000 to about 8500, and an even more preferred range is from about4000 to about 8000. The weight average molecular weight should be atleast about 30,000, preferably at least about 100,000. The weightaverage molecular weight is preferably up to about 60 million, basedupon a GPC determination using an available standard having 6 millionweight average molecular weight. A preferred range for M_(w) is fromabout 30,000 to about 55 million, a more preferred range for M_(w) isfrom about 100,000 to about 1 million, and a still more preferred rangeis from about 100,000 to about 300,000. Resins having ultra-highmolecular weight shoulders (above about 45 million), which can be seenby GPC, are preferably avoided for the M_(w) range of from about 100,000to about 300,000. The polydispersity, or ratio of M_(w)/M_(n), may be upto about 10,000, preferably up to about 1000. The polydispersity ispreferably at least about 15, particularly preferably at least about 50.The polydispersity preferably falls in the range of from about 15 toabout 1000, and more preferably it falls in a range of from about 50 toabout 800.

[0043] The theoretical glass transition temperature (T_(g)) can beadjusted according to methods well-known in the art through selectionand apportionment of the co-monomers. In a preferred embodiment, thetheoretical T_(g) is above room temperature, and preferably thetheoretical T_(g) is at least about 60° C., more preferably at leastabout 70° C. The methods and compositions of the present inventionpreferably employ vinyl polymers having a T_(g) of from about 50° C. toabout 125° C., more preferably from about 60° C. to about 100° C., andeven more preferably from about 70° C. to about 90° C. The theoreticalglass transition temperature can be determined using the Fox equation.

[0044] In one embodiment of the invention, the hydrogen bonding vinylpolymer, which may be a branched vinyl polymer, is combined with otherresins in the ink composition. Examples of suitable other resins thatmay be combined with the hydrogen bonding vinyl polymer include, withoutlimitation, polyester and alkyd resins, phenolic resins, rosins,cellulosics, and derivatives of these such as rosin-modified phenolics,phenolic-modified rosins, hydrocarbon-modified rosins, maleic modifiedrosin, fumaric modified rosins; hydrocarbon resins, other acrylic orvinyl resins, polyamide resins, and so on. When present, such resins orpolymers may be included in amounts of from about 1 part by weight up toabout 100 parts by weight, preferably about 3 to about 50 parts byweight, for each part by weight of the hydrogen bonding vinyl polymer ofthe invention, based upon the nonvolatile weights of the resins.

[0045] In addition to the hydrogen bonding vinyl resin and any optionalsecond resin, the ink compositions of the invention preferably includeone or more organic solvents. In a preferred embodiment of theinvention, the branched vinyl resin forms a solution or apparentsolution having no apparent turbidity in the organic solvent or solventsof the ink formulation. The particular organic solvents and amount ofsolvent included is determined by the ink viscosity, body, and tackdesired. In general, non-oxygenated solvents or solvents with lowKauri-butanol (KB) values are used for inks that will be in contact withrubber parts such as rubber rollers during the lithographic process, toavoid affecting the rubber. Suitable solvents for inks that will contactrubber parts include, without limitation, aliphatic hydrocarbons such aspetroleum distillate fractions and normal and isoparaffinic solventswith limited aromatic character. For example, petroleum middledistillate fractions such as those available under the tradename MagieSol, available from Magie Bros. Oil Company, a subsidiary ofPennsylvania Refining Company, Franklin Park, Ill., under the tradenameExxPrint, available from Exxon Chemical Co., Houston, Tex., and fromGolden Bear Oil Specialties, Oildale, Calif., Total Petroleum Inc.,Denver, Colo., and Calumet Lubricants Co., Indianapolis, Ind. may beused. In addition or alternatively, soybean oil or other vegetable oilsmay be included.

[0046] When non-oxygenated solvents such as these are used, it isgenerally necessary to include a sufficient amount of at least onemonomer having a substantial affinity for aliphatic solvents in order toobtain the desired solvency of the preferred branched vinyl polymer. Ingeneral, acrylic ester monomers having at least six carbons in thealcohol portion of the ester or styrene or alkylated styrene, such astert-butyl styrene, may be included in the polymerized monomers for thispurpose. In a preferred embodiment, an ink composition withnon-oxygenated solvents includes a branched vinyl resin polymerized froma monomer mixture including at least about 20%, preferably from about20% to about 40%, and more preferably from about 20% to about 25% of amonomer that promotes aliphatic solubility such as stearyl methacrylateor t-butyl styrene, with stearyl methacrylate being a preferred suchmonomer. It is also preferred to include at least about 55% percentstyrene, preferably from about 55% to about 80% styrene, and morepreferably from about 60% to about 70% styrene. Other monomers may alsobe used to reduce solvent tolerance in aliphatic solvent, if desired.All percentages are by weight, based upon the total weight of themonomer mixture polymerized. Among preferred monomer compositions forvinyl polymers for lithographic inks are those including a (meth)acrylicester of an alcohol having 8-20 carbon atoms such as stearylmethacrylate, styrene, divinylbenzene, and a monomer containing hydrogenbonding groups. In a preferred embodiment, a branched vinyl resin for alithographic printing ink is made with from about 15, preferably about20, to about 30, preferably about 25, weight percent of a (meth)acrylicester of an alcohol having 8-20 carbon atoms, especially stearylmethacrylate; from about 50, preferably about 60, to about 80,preferably about 75, weight percent of a styrenic monomer, especiallystyrene itself.

[0047] Preferably, the organic solvent or solvent mixture will have aboiling point of at least about 100° C. and preferably not more thanabout 550° C. Offset printing inks may use solvents with boiling pointabove about 200° C. News inks usually are formulated with from about 20to about 85 percent by weight of solvents such as mineral oils,vegetable oils, and high boiling petroleum distillates. The amount ofsolvent also varies according to the type of ink composition (that is,whether the ink is for newsprint, heatset, sheetfed, etc.), the specificsolvents used, and other factors known in the art. Typically the solventcontent for lithographic inks is up to about 60%, which may include oilsas part of the solvent package. Usually, at least about 35% solvent ispresent in lithographic ink. When used to formulate the preferred inkcompositions of the invention, these varnishes or vehicles, includingthe branched vinyl resins, are typically clear, apparent solutions.

[0048] The ink compositions of the invention will usually include one ormore pigments in the hydrophobic phase. The number and kinds of pigmentswill depend upon the kind of ink being formulated. News ink, cold set,and book black compositions typically will include only one or only afew pigments, such as carbon black, while custom color inks may includea more complicated pigment package, including colors with specialeffects such as pearlescence or metallic effect. Lithographic printinginks for full-color printing are typically used in four colors—magenta,yellow, black, and cyan, and custom colors may be included as desired.Any of the customary inorganic and organic pigments may be used in theink compositions of the present invention. Alternatively, thecompositions of the invention may be used as overprint lacquers orvarnishes. The overprint lacquers (air drying) or varnishes (curing) areintended to be clear or transparent and thus opaque pigments are notincluded.

[0049] It has been observed that the print quality using lithographicink compositions of the invention can be a function of pH under certainconditions. As noted above, a wide variety of chemical functional groupsin the hydrogen bonding vinyl resin are suitable to provide lithographicsingle fluid ink compositions that are stable in the fountain and breakwhen applied to the printing plate to provide high quality printedmaterials. It is believed that the invention operates in part on theprinciple of a balance between hydrogen donating ability and hydrogenaccepting ability between the hydrogen bonding groups of the vinyl resinand the components of the hydrophilic fluid phase. The components of thehydrophilic fluid phase contain hydroxyl groups that have both hydrogendonating ability and hydrogen accepting ability. Depending on thehydrogen bonding vinyl resin chosen for the ink compositions of theinvention, hydrogen bonding groups on the vinyl resin may haverelatively higher or lower hydrogen donating or accepting ability. Ifthe hydrogen bonding group on the polymer is relatively lower inhydrogen donating ability, then it may be preferred to put a componentinto the hydrophilic fluid phase to increase its relative hydrogenaccepting ability to provide the proper balance. For example, when thehydrogen bonding group on the polymer is an alcohol, it has been founduseful to add a weak base to the hydrophilic fluid phase. On the otherhand, when the hydrogen bonding functional group on the vinyl resin isan especially strong hydrogen acceptor, care must be taken not to putadditives into the hydrophilic fluid phase that would increase thehydrogen donating ability of the hydrophilic fluid phase. For example,when the hydrogen bonding group on the vinyl resin is an amine group, itis preferred not to put a weak acid into the hydrophilic fluid phase.Such a weak acid in the hydrophilic fluid phase would tend to form asalt with the amine on the vinyl resin, leading to poor performance ofthe ink composition, since the composition would be too stabilized bythe ionic pair to break upon application to the printing plate. Inkscontaining vinyl resins with amine functional groups as discussed aboveare most effective at approximately a neutral pH.

[0050] When the hydrogen bonding functional group on the vinyl resin isan amide or an N-alkylamide, it has been observed that the properfunctioning of the ink composition is nearly independent of pH. It isbelieved that the amide functional group has a proper balance ofhydrogen accepting properties so as to accommodate either a low pH, highpH, or neutrality in the hydrophilic fluid phase. In contrast, forhydrogen bonding vinyl resins containing alcohol hydrogen bondinggroups, the performance of the ink composition is dependent on the pH.

[0051] It is preferred that the hydrophilic fluid phase have Hansensolubility parameters having these values: a dispersion parameter valueof at least about 6, a polarity parameter value of at least about 4, anda hydrogen bonding parameter value of at least about 10. Preferably, thehydrophilic fluid phase has Hansen solubility parameters having thesevalues: a dispersion parameter value of from about 8.0 to about 9.0, apolarity parameter value of from about 5.0 to about 8.0, and a hydrogenbonding parameter value of from about 12 to about 20.

[0052] At least a small amount of water is often desirable in order toaid in dissolving or homogenizing the ingredients of the hydrophilicfluid phase. In general, about 4 or 5% by weight of water may beincluded in the hydrophilic fluid phase for this purpose. When water ispresent in higher amounts, and especially when the hydrophilic fluidphase is more than 50% water, adjustments are generally necessary toobtain satisfactory inks. For example, organic or inorganic salts shouldbe added to the hydrophilic fluid phase to maintain the integrity of theemulsion. Such salts include, without limitation, monovalent or divalentsalts that are at least partially soluble in the hydrophilic fluidphase. Examples of such salts include, without limitation, as lithium,sodium, potassium, magnesium, calcium, iron(II), manganese(II),copper(II), and zinc salts, particularly the acetates, hydroxyacetates,nitrates, sulfates, phosphates, hydrogen phosphates, hydrogen sulfates,chlorates, chlorides, bromides, and iodides of these metals, and thelike. Such salts may be included in the hydrophilic fluid phase at up toabout 5% by weight, preferably from about 0.01% to about 5% by weight,more preferably from about 0.1% to about 1.5% by weight. In addition,when the hydrophilic fluid phase contains more than about 5% water, anychemical groups that can participate in a hydrogen bond in the inkvehicles (such as the commonly used acid functional alkyd vehicles)should be used in lesser amounts. A wetting agent, such aspolyvinylpyrrolidone, may be added to aid in wetting of the plate. Fromabout 0.5 weight percent to about 1.5 weight percent of thepolyvinylpyrrolidone is included, based on the weight of the inkcomposition.

[0053] It will be appreciated by the skilled artisan that otheradditives known in the art may be included in the ink compositions ofthe invention, so long as such additives do not significantly detractfrom the benefits of the present invention. Illustrative examples ofthese include, without limitation, pour point depressants, surfactants,wetting agents, waxes, emulsifying agents and dispersing agents,defoamers, antioxidants, UV absorbers, dryers (e.g., for formulationscontaining vegetable oils), flow agents and other rheology modifiers,gloss enhancers, and anti-settling agents. When included, additives aretypically included in amounts of at least about 0.001% of the inkcomposition, and may be included in amount of about 7% by weight or moreof the ink composition.

[0054] The compositions of the invention are suited for any lithographicapplications, including, without limitation, as heats,et inks, newsinks, and sheetfed inks. Offset printing processes in general in whichthe inks of the invention may be used are well-known in the art and aredescribed in many publications.

[0055] The invention is illustrated by the following examples. Theexamples are merely illustrative and do not in any way limit the scopeof the invention as described and claimed. All parts are parts by weightunless otherwise noted.

EXAMPLES

[0056] In the Examples, t-BICM75 is a 75% solution oft-butylperoxyisopropyl carbonate in mineral spirits.

Example 1 Preparation of a Hydrogen bonding Vinyl/Resin with CarboxylGroups

[0057] An amount of 44.19 parts by weight of Total 220 (a petroleummiddle distillate fraction available from Total Petroleum, Inc.) ischarged to a glass reactor equipped with stirrer, nitrogen inlet, totalreflux condenser, and monomer inlet. The solvent is heated to 160° C.with stirring under a blanket of nitrogen. A monomer mixture of 36.01parts by weight styrene, 12.27 parts by weight stearyl methacrylate,2.62 parts by weight divinylbenzene, 1.89 parts by weight methacrylicacid, and 2.79 parts by weight t-BICM75 is added to the reactor over aperiod of three hours. After the monomer addition is complete, 0.23parts by weight of t-BICM75 is added over a period of fifteen minutes.The temperature is held at 160° C. for an additional two hours to allowfor complete conversion of the monomer to polymer. The measured amountof non-volatile matter (NVM) is 55%. The percent conversion, measured asNVM divided by the percent of the total weight of monomers, is 100.1.The acid number on solution is 12.0 mg KOH per gram. The viscosity is 30Stokes (bubble tube, 54.4° C.). The solvent tolerance is 230% and theNVM at cloud point is 16.7%.

Example 2 Preparation of a Hydrogen bonding Vinyl Resin with CarboxylGroups

[0058] An amount of 44.22 parts by weight of Golden Bear 1108 (apetroleum middle distillate fraction available from Golden Bear OilSpecialties) is charged to a reaction flask equipped with stirrer,nitrogen inlet, total reflux condenser, and monomer inlet. The solventwas heated to 145° C. with stirring. A monomer mixture of 33.86 parts byweight styrene, 12.6 parts by weight stearyl methacrylate, 3.1 parts byweight n-butyl acrylate, 1.31 parts by weight divinylbenzene HP (80%divinylbenzene), 1.89 parts by weight methacrylic acid, and 2.89 partsby weight t-BICM75 is added to the reaction flask over a period of 3hours. After the monomer addition is complete, 0.23 parts by weight oft-BICM75 is added to the flask over a period of 15 minutes. Thetemperature is held at 145° C. for an additional two hours to allow forcomplete conversion of the monomer to polymer. The measured amount ofnon-volatile matter (NVM) is 56%. The percent conversion, measured asthe percent of the total weight of monomers converted to non-volatilematter is 101.5. The acid number on solution is 12.0 mg KOH per gram.The viscosity is 47 Stokes (bubble tube, 54.4° C.). The solventtolerance is greater than 1400% and the NVM at cloud point is less than3.7% (i.e., no cloud point is observed yet at this dilution).

Example 3 Preparation of a Hydrogen bonding Vinyl Resin with CarboxylGroups

[0059] An amount of 461.2 parts by weight of Calumet 600 (a petroleummiddle distillate fraction available from Calumet Lubricants Co.) ischarged to a glass reactor equipped with stirrer, nitrogen inlet, totalreflux condenser, and monomer inlet. The solvent is heated to 145° C.with stirring under a blanket of nitrogen. A monomer mixture of 350.1parts by weight styrene, 131.3 parts by weight stearyl methacrylate,42.1 parts by weight n-butyl acrylate, 17.1 parts by weightdivinylbenzene HP, 9.8 parts by weight methacrylic acid, and 29.2 partsby weight t-BICM75 is added to the reactor over a period of three hours.After the monomer addition is complete, 2.4 parts by weight of t-BICM75is added over a period of fifteen minutes. The temperature is held at145° C. for an additional two hours to allow for complete conversion ofthe monomer to polymer. The measured amount of non-volatile matter (NVM)is 56%. The percent conversion, measured as NVM divided by the percentof the total weight of monomers, is 101.6. The acid number on solutionis 6.3 mg KOH per gram. The viscosity is 35 Stokes (bubble tube, 54.4°C.). The solvent tolerance is 80% and the NVM at cloud point is 31.0%.

Example 4 Preparation of a Vinyl Resin Without Hydrogen Bonding Groupsfor Comparative Testing

[0060] An amount of 1548.1 parts by weight of ExxPrint 283D (a petroleummiddle distillate fraction available from Exxon Chemical Co.) is chargedto a glass reactor equipped with stirrer, nitrogen inlet, total refluxcondenser, and monomer inlet. The solvent is heated to 145° C. withstirring under a blanket of nitrogen. A monomer mixture of 1248.5 partsby weight styrene, 429.6 parts by weight stearyl methacrylate, 102.8parts by weight n-butyl acrylate, 68.9 parts by weight divinylbenzeneHP, and 85.7 parts by weight t-BICM75 is added to the reactor over aperiod of three hours. After the monomer addition is complete, 16.4parts by weight of t-BICM75 is added over a period of fifteen minutes.The temperature is held at 145° C. for an additional two hours to allowfor complete conversion of the monomer to polymer. The measured amountof non-volatile matter (NVM) is 56%. The percent conversion, measured asNVM divided by the percent of the total weight of monomers, is 101.4.The viscosity is 26 Stokes (bubble tube, 54.4° C.). The solventtolerance is 160% and the NVM at cloud point is 21.5%.

Example 5 Preparation of a Heatset Single Fluid Printing Ink Accordingto the Invention

[0061] 58.0 grams of the following Mixture 5A is added to 142.0 grams ofthe following Mixture 5B with stirring. The ink composition is mixed for20 minutes on a dispersator, maintaining a vortex and holding thetemperature under 140° F. The ink composition has a single fall timeLaray of 14 to 17 seconds for 500 grams at 30° C. When used in asingle-fluid heatset lithographic printing process, the ink printswithout toning.

[0062] Mixture 5A

[0063] Mix in a glass beaker until clear 181.0 grams of diethyleneglycol, 8.0 grams of deionized water, 0.4 grams of citric acid, and 0.4grams of magnesium nitrate. Add 191.2 grams of diethylene glycol and mixuntil homogenous.

[0064] Mixture 5B

[0065] Mix, using a high-speed mixer, 46.0 grams of the vinyl vehicle ofExample 1, 4.0 grams of Blue Flush 12-FH-320 (available from CDRCorporation, Elizabethtown, Ky.) 1.0 gram technical grade Soy oil(available from Cargill, Chicago, Ill.) and 0.6 grams of an antioxidant.While mixing, add 34.4 grams of a hydrocarbon resin solution (60%LX-2600 in ExxPrint 283D, available from Neville), 27.0 grams of acarbon black (CSX-156 available from Cabot Corp.), and 1.0 gram of apolytetrafluoroethylene wax (Pinnacle 9500D, available from CarrolScientific). Mix at a high speed for 30 minutes at 300° F. Slow themixing speed and add 27.0 grams of ExxPrint 588D (available from Exxon).Mill the premix in a shot mill to a suitable grind. Mixture B has aLaray viscosity of 180 to 240 poise and a Laray yield of 800 to 1200(according to test method ASTM D-4040: Power Law-3 k, 1.5 k, 0.7 k, 0.3k). Mixture 5B is tested on the Inkometer for one minute at 1200 rpm fora measured result of 25 to 29 units.

Example 6 Preparation of a News Ink Single Fluid Printing Ink Accordingto the Invention

[0066] Mixture 6A

[0067] A mixture of 87.0 grams of diethylene glycol, 12.7 grams ofglycerin, 0.15 gram of citric acid monohydrate, and 0.15 grams ofmagnesium nitrate hexahydrate is stirred with heat (at 130-140° F.)until homogenous.

[0068] Mixture 6B

[0069] A blend of 40.2 grams of a gilsonite varnish, 0.8 gram oronite,17.9 grams MSO solvent (available from Calumet), and 41.1 grams of acarbon black (CSX-320 from Cabot Corp.) were mixed with shear to a 4.0on the Hegman grind gauge, and then ground in a shot mill to a grind ona 2 mil gauge of at least 0/10. The Laray viscosity at 30° C. ismeasured as 296 poise for a drop with 2000 grams of added weight and as1332 poise for a drop with 200 grams of added weight (±25% accuracy) andgives an inkometer reading at 90° F. (32° C.) for 1 minute at 400 rpmfollowed immediately by 1 minute at 1200 rpm of 5-10 units.

[0070] News Ink

[0071] The news ink is prepared by mixing together 32.4 grams of themixture B and 37.6 grams of Example 2 to obtain a Mixture 6C having aninkometer reading at 90° F. (32° C.) for 1 minute at 400 rpm followedimmediately by 1 minute at 1200 rpm of 18.8 units, a Laray viscosity at30° C. of 375 poise for a drop with 2000 grams of added weight and 565poise for a drop with 200 grams of added weight (±25% accuracy), and aviscosity as measured according to ASTM D4040 (power law 2000, 1500,1000, 500) at 2500 s⁻¹ of 285 poise with a pseudo yield of 1709 dynesper cm². To obtain the ink, 30.0 grams of Mixture 6A is added to Mixture6C with mixing at 3000 rpm for 10 minutes. The resulting ink has asingle fall time Laray at 30° C. of 21 seconds for 500 grams. The inkdid not exhibit toning when using in a single-fluid lithographicprinting process.

Example 7 Synthesis of a Hydrogen bonding Vinyl Resin ContainingHydroxyl Groups

[0072] Solvent ExxPrint 274A, 461.5 grams, was charged to a reactorequipped with a stirrer, a nitrogen inlet, a total condenser and aninlet port. A monomer/initiator blend of 371.5 grams styrene, 1126.5grams stearyl methacrylate, 23.9 grams divinylbenzene HP, 29.8 gramshydroxypropyl methacrylate, and 27.7 grams of t-BICM75 was charged tothe reactor through the inlet port over a period of two hours and 15minutes. During addition, the temperature was maintained at 160° C. andthe reactor was blanketed with nitrogen. After addition, 2.5 grams oft-BICM75 were added, and the reaction was run for an additional twohours. The reaction product was poured through a fine strainer into acontainer for storage. The measured amount of non-volatile material(NVM) was 56.2%. The percent conversion, measured as the percent of thetotal weight of monomers converted to non-volatile matter, was 102.2.The viscosity was 12.6 stokes (bubble tube 54.4° C.). The solventtolerance was 380% and the NVM at cloud point was 11.7%.

Example 8 Synthesis of a Hydrogen bonding Vinyl Resin Containing AmideGroups

[0073] Solvent ExxPrint 274A, 461.5 grams, was charged into a reactorequipped with a stirrer nitrogen inlet total condenser and inlet portand heated with stirring to 160° C. A monomer initiator blend containing376.8 grams styrene, 128.3 grams stearyl methacrylate, 23.9 gramsdivinylbenzene HP, 22.7 grams N,N-dimethyl acrylamide, and 27.7 gramst-BICM75 was charged through the inlet port over a period of 2 hours and15 minutes during which time the temperature was maintained withstirring at 160° C. and the reactor was blanketed with nitrogen. Afterthe addition was completed, 2.5 grams of t-BICM75 was added and thereaction continued for an additional 2 hours. The measured amount ofnon-volatile matter (NVM) was 56.6%. The percent conversion was 103.0.The viscosity was 23.5 stokes at 54.4° C. The solvent tolerance was 688%and the NVM at cloud point was less than 8.2%.

Example 9

[0074] Using a high speed mixer, 118 grams of the hydrogen bonding vinylresin of Example 8 were mixed with 102.5 grams of blue flush 15 FQ-308(containing phthalocyanine blue, available from CDR Corporation,Elizabethtown, Ky.), 16.5 grams of alkyl refined linseed oil, and 5grams of a Teflon wax. While mixing, 116.5 grams of a hydrocarbon resinsolution (60% Lx-2600 in ExxPrint 283D, available from Neville) wasadded and mixed at a high speed for 30 minutes at 160° F. to form amixture 9b. The mixing speed was slowed and 28.3 parts by weight ofmixture 5a was added to 71.7 parts by weight of mixture 9b. The finishedviscosity of the ink (cone in plate rheometer) at 30° C. was 178.3 Pa s.

[0075] The ink was tested for stability and toning in a lithographicprinting process. The fountain stability of the ink was greater than 900seconds, and the ink printed with no toning.

Example 10 Preparation of an Ink Containing an Amide Functional VinylResin

[0076] Mixture 10a was formed by mixing in a glass beaker until clear181 grams of diethylene glycol, 8 grams of deionized water, 0.4 gramstriethanolamine, and 0.4 grams of magnesium nitrate. To this was, added191.2 grams of ethylene glycol and mixed until homogeneous.

[0077] Using a high speed mixer 118 grams of the hydrogen bonding vinylresin of Example 7 was mixed with 102.5 grams of blue flush 15 FQ-308(containing phthalocyanine blue, available from CDR Corporation,Elizabethtown, Ky.), 16.5 grams of alkyl refined linseed oil, and 5grams of a Teflon wax. With mixing, 116.5 grams of a hydrocarbon resinsolution (60% LX-2600 in ExxPrint 283D, available from Neville) wasadded and mixed at a high speed for 30 minutes at 160° F. to form amixture 10b.

[0078] To make the ink, 28.3 parts by weight of mixture 10a was mixedwith 71.7 parts of mixture 10b. The finished viscosity of the ink (conein plate rheometer) at 30° C. was 101.8 Pa s.

[0079] The ink was tested for stability and toning in a lithographicprinting process. The fountain stability of the ink was greater than 900seconds, and the ink printed with no toning.

Examples 11-16 and Comparative Examples A-D

[0080] Examples 11-16 and comparative examples A-D were prepared by amethod similar to that of Example 5 with the components and the amountof components as listed in the following table. The Examples were testedfor stability in a fountain solution, and for toning in a lithographicprinting process. Examples 11-13 were made with the acid functionalvinyl resin of Example 1 while Examples 14-16 were made with the acidfunctional vinyl resin of Example 3. The hydrophilic phase of allExamples 11-16 contained the diethylene glycol, ethylene glycol andwater mixture of Example 5A, further containing citric acid andmagnesium nitrate. In the comparative examples, inks were run inlithographic printing processes that did not contain the hydrogenbonding vinyl resins of the invention. Comparative Examples A-Ccontained the vinyl resin of Example 4, which contains no functionalgroups capable of forming hydrogen bonds to the components of thehydrophilic phase. Comparative Example D was run on an ink made of aconventional rosin modified hydrocarbon solution. In the case ofcomparative Examples A-C, the ink was not stable in the fountain and wasnot stable enough to run in the printing process. Comparative Example Dwas stable enough to run in the printing process, but it exhibitedtoning on the first sheet printed. Example Example Example ExampleExample Example Material 11 12 13 14 15 16 Acid-functional vinyl 8 18 37resin of Example 1 Acid-functional vinyl 8 18 37 resin of Example 3Hydrocarbon 32.5 22.5 32.5 22.5 varnish solution¹ Uncoated black 30 3030 30 30 30 base² Total 220 0.5 0.5 4 0.5 0.5 4 Diethylene glycol 29 2929 29 29 29 mix³ Fountain Break >600 >600 >600 >600 >600 >600 Time(seconds) Tone Clean Clean Clean Clean Clean Clean

[0081] Comparative Comparative Comparative Comparative Material ExampleA Example B Example C Example D Vinyl resin of 8 18 37 Example 4 Rosinmodified 37 hydrocarbon solution⁴ (acid number of 4.8 on solutionHydrocarbon 32.5 22.5 varnish solution¹ Uncoated black 30 30 30 30 base²Total 220 0.5 0.5 4 4 Diethylene 29 29 29 29 glycol mix³ Fountain Break200 60 5 >600 Time (seconds) Tone (not stable (not stable (not stableImmediate enough to enough to enough to (tones on run) run) run) firstsheet)

[0082] The invention has been described in detail with reference topreferred embodiments thereof. It should be understood, however, thatvariations and modifications can be made within the spirit and scope ofthe invention and of the following claims.

What is claimed is:
 1. A lithographic ink composition, comprising acontinuous phase comprising a hydrogen bonding vinyl polymer and anemulsified phase comprising a member selected from the group consistingof water, liquid polyols, and combinations thereof.
 2. A lithographicink composition according to claim 1, wherein the emulsified phasecomprises a liquid polyol is selected from the group consisting ofethylene glycol, diethylene glycol, triethylene glycol, tetraethyleneglycol, propylene glycol, dipropylene glycol, 1,3-propanediol,dipropylene glycol, 1,4-butanediol, glycerol, and mixtures thereof.
 3. Alithographic ink composition according to claim 1, wherein the inkcomposition includes from about 5% to about 50% of the emulsified phaseby weight.
 4. A lithographic ink composition according to claim 1,wherein the ink composition includes from about 10% to about 35% of theemulsified phase by weight.
 5. A lithographic ink composition accordingto claim 1, wherein the ink composition includes from about 20% to about30% of the emulsified phase by weight.
 6. A lithographic ink compositionaccording to claim 1, wherein the emulsified phase includes a weak acidor a weak base.
 7. A lithographic ink composition according to claim 1,wherein the emulsified phase includes a member selected from the groupconsisting of lithium, sodium, potassium, magnesium, calcium, iron(II),manganese(II), copper(II), and zinc acetates, hydroxyacetates, nitrates,sulfates, phosphates, hydrogen phosphates, hydrogen sulfates, chlorates,chlorides, bromides, iodides, and combinations thereof.
 8. Alithographic ink composition according to claim 1, wherein theemulsified phase is nonaqueous.
 9. A lithographic ink compositionaccording to claim 1, wherein the emulsified phase comprises both waterand a liquid polyol.
 10. A lithographic ink composition according toclaim 1, wherein the emulsified phase comprises a mixture of liquidpolyols.
 11. A lithographic ink composition according to claim 1,wherein the emulsified phase further comprises at least one solidpolyol.
 12. A lithographic ink composition according to claim 1, whereinthe emulsified phase comprises a member selected from the groupconsisting of 2,3-butanediol, hexanediols, pentaerythritol,dipentaerythritol, hydroxyl-functional hyperbranched dendrimers,trimethylolethane, trimethylolpropane, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, hydrogenatedbisphenol A, compounds having one hydroxyl group and up to about 18carbon atoms, and combinations thereof.
 13. A lithographic inkcomposition according to claim 1, wherein the emulsified phase comprisesa member selected from the group consisting of citric acid, tartaricacid, tannic acid, and combinations thereof.
 14. A lithographic inkcomposition according to claim 1, wherein the emulsified phase comprisestriethanolamine.
 15. A lithographic ink composition according to claim1, wherein the emulsified phase comprises from about 0.01 weight percentto about 2 weight percent of a weak acid or a weak base.
 16. Alithographic ink composition according to claim 1, wherein theemulsified phase comprises from about 0.01 weight percent to about 0.5weight percent of magnesium nitrate.
 17. A lithographic ink compositionaccording to claim 1, wherein the emulsified phase comprises a watersoluble polymer.
 18. A lithographic ink composition according to claim1, wherein the emulsified phase comprises a member selected from thegroup consisting of poly(vinyl pyrrolidone), poly(vinyl alcohol),poly(ethylene glycol), and combinations thereof.
 19. A lithographic inkcomposition according to claim 1, wherein the hydrogen bonding vinylpolymer comprises hydrogen bonding groups selected from the groupconsisting of carboxylic acid groups, carboxylic anhydride groups,primary amine groups, amine groups having N-alkyl substituents of threeor fewer carbon atoms, primary amide groups, amide groups having N-alkylsubstituents of three or fewer carbon atoms, ester groups having pendantalkyl groups of three or fewer carbon atoms, β-hydroxyl ester groups,hydroxyl groups, sulfur-containing groups, phosphorous-containinggroups, acetoacetate groups, and combinations thereof.
 20. Alithographic ink composition according to claim 1, wherein the hydrogenbonding vinyl polymer comprises primary amine groups, amine groupshaving N-alkyl substituents of three or fewer carbon atoms, orcombinations thereof.
 21. A lithographic ink composition according toclaim 1, wherein the hydrogen bonding vinyl polymer comprises primaryamide groups, amide groups having N-alkyl substituents of three or fewercarbon atoms, or combinations thereof.
 22. A lithographic inkcomposition according to claim 1, wherein the hydrogen bonding vinylpolymer comprises hydroxyl groups.
 23. A lithographic ink compositionaccording to claim 1, wherein the hydrogen bonding vinyl polymercomprises carboxylic acid groups, carboxylic anhydride groups, orcombinations thereof.
 24. A lithographic ink composition according toclaim 1, wherein the hydrogen bonding vinyl polymer comprises estergroups having pendant alkyl groups of three or fewer carbon atoms,β-hydroxyl ester groups, or combinations thereof.
 25. A lithographic inkcomposition according to claim 1, wherein the hydrogen bonding vinylpolymer comprises sulfur-containing groups.
 26. A lithographic inkcomposition according to claim 1, wherein the hydrogen bonding vinylpolymer comprises hydrogen bonding groups selected from the groupconsisting of sulfonic acid groups, sulfonamide groups, sulfoxidegroups, sulfone groups, mercapto groups, phosphoric acid groups,phosphate groups, phosphonamide groups, and combinations thereof.
 27. Alithographic ink composition according to claim 1, wherein the hydrogenbonding vinyl polymer comprises vinyl alcohol monomeric units.
 28. Alithographic ink composition according to claim 22, wherein theemulsified phase includes a weak base.
 29. A lithographic inkcomposition according to claim 1, wherein the hydrogen bonding vinylpolymer comprises a combination of different hydrogen bonding groups.30. A lithographic ink composition according to claim 1, wherein thehydrogen bonding groups of the hydrogen bonding vinyl polymer functionas hydrogen donating groups.
 31. A lithographic ink compositionaccording to claim 1, wherein the hydrogen bonding groups of thehydrogen bonding vinyl polymer function as hydrogen accepting groups.32. A lithographic ink composition according to claim 1, wherein thehydrogen bonding groups of the hydrogen bonding vinyl polymer functionas both hydrogen donating and hydrogen accepting groups.
 33. Alithographic ink composition according to claim 30, wherein theemulsified phase includes a weak base.
 34. A lithographic inkcomposition according to claim 31, wherein the emulsified phase includesa weak acid.
 35. A lithographic ink composition according to claim 1,wherein the hydrogen bonding vinyl polymer has an equivalent weight,based on hydrogen bonding groups, of at least about 1800 grams perequivalent.
 36. A lithographic ink composition according to claim 1,wherein the hydrogen bonding vinyl polymer has an equivalent weight,based on hydrogen bonding groups, of up to about 20,000 grams perequivalent.
 37. A lithographic ink composition according to claim 1,wherein the hydrogen bonding vinyl polymer has an equivalent weight,based on hydrogen bonding groups, of from about 2200 grams perequivalent to about 7200 grams per equivalent.
 38. A lithographic inkcomposition according to claim 1, wherein the hydrogen bonding vinylpolymer comprises acetoacetate groups.
 39. A lithographic inkcomposition, comprising a hydrophobic, continuous phase comprising asolution of a branched, hydrogen bonding vinyl polymer and an emulsifiedphase comprising a member selected from the group consisting of water,liquid polyols, and combinations thereof.
 40. A lithographic inkcomposition according to claim 39, wherein the emulsified phasecomprises a liquid polyol is selected from the group consisting ofethylene glycol, diethylene glycol, triethylene glycol, tetraethyleneglycol, propylene glycol, dipropylene glycol, 1,3-propanediol,1,4-butanediol, glycerol, and mixtures thereof.
 41. A lithographic inkcomposition according to claim 39, wherein the ink composition includesfrom about 5% to about 50% of the emulsified phase by weight.
 42. Alithographic ink composition according to claim 39, wherein the inkcomposition includes from about 10% to about 35% of the emulsified phaseby weight.
 43. A lithographic ink composition according to claim 39,wherein the emulsified phase includes a member selected from the groupconsisting of lithium, sodium, potassium, magnesium, calcium, iron(II),manganese(II), copper(II), and zinc acetates, hydroxyacetates, nitrates,sulfates, phosphates, hydrogen phosphates, hydrogen sulfates, chlorates,chlorides, bromides, iodides, and combinations thereof.
 44. Alithographic ink composition according to claim 39, wherein theemulsified phase is nonaqueous.
 45. A lithographic ink compositionaccording to claim 39, wherein the emulsified phase comprises both waterand a liquid polyol.
 46. A lithographic ink composition according toclaim 39, wherein the emulsified phase comprises a mixture of liquidpolyols.
 47. A lithographic ink composition according to claim 39,wherein the emulsified phase further comprises at least one solidpolyol.
 48. A lithographic ink composition according to claim 39,wherein the emulsified phase comprises a member selected from the groupconsisting of 2,3-butanediol, hexanediols, pentaerythritol,dipentaerythritol, hydroxyl-functional hyperbranched dendrimers,trimethylolethane, trimethylolpropane, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, hydrogenatedbisphenol A, compounds having one hydroxyl group and up to about 18carbon atoms, and combinations thereof.
 49. A lithographic inkcomposition according to claim 39, wherein the emulsified phasecomprises from about 0.01 weight percent to about 2 weight percent of aweak acid or a weak base.
 50. A lithographic ink composition accordingto claim 39, wherein the emulsified phase comprises a wetting agent. 51.A lithographic ink composition according to claim 39, wherein thehydrogen bonding vinyl polymer comprises hydrogen bonding groupsselected from the group consisting of carboxylic acid groups, carboxylicanhydride groups, primary amine groups, amine groups having N-alkylsubstituents of three or fewer carbon atoms, primary amide groups, amidegroups having N-alkyl substituents of three or fewer carbon atoms, estergroups having pendant alkyl groups of three or fewer carbon atoms,β-hydroxyl ester groups, hydroxyl groups sulfur-containing groups,phosphorous-containing groups, acetoacetate groups, and combinationsthereof.
 52. A lithographic ink composition according to claim 39,wherein the hydrogen bonding vinyl polymer comprises primary aminegroups, amine groups having N-alkyl substituents of three or fewercarbon atoms, or combinations thereof.
 53. A lithographic inkcomposition according to claim 39, wherein the hydrogen bonding vinylpolymer comprises primary amide groups, amide groups having N-alkylsubstituents of three or fewer carbon atoms, or combinations thereof.54. A lithographic ink composition according to claim 39, wherein thehydrogen bonding vinyl polymer comprises hydroxyl groups.
 55. Alithographic ink composition according to claim 39, wherein the hydrogenbonding vinyl polymer comprises carboxylic acid groups, carboxylicanhydride groups, or combinations thereof.
 56. A lithographic inkcomposition according to claim 39, wherein the hydrogen bonding vinylpolymer comprises ester groups having pendant alkyl groups of three orfewer carbon atoms, β-hydroxyl ester groups, or combinations thereof.57. A lithographic ink composition according to claim 39, wherein thehydrogen bonding vinyl polymer comprises sulfur-containing groups.
 58. Alithographic ink composition according to claim 39, wherein theemulsified phase includes a weak base.
 59. A lithographic inkcomposition according to claim 39, wherein the hydrogen bonding vinylpolymer comprises a combination of different hydrogen bonding groups.60. A lithographic ink composition according to claim 39, wherein thehydrogen bonding groups of the hydrogen bonding vinyl polymer functionas hydrogen donating groups.
 61. A lithographic ink compositionaccording to claim 39, wherein the hydrogen bonding groups of thehydrogen bonding vinyl polymer function as hydrogen accepting groups.62. A lithographic ink composition according to claim 39, wherein thehydrogen bonding groups of the hydrogen bonding vinyl polymer functionas both hydrogen donating and hydrogen accepting groups.
 63. Alithographic ink composition according to claim 60, wherein theemulsified phase includes a weak base.
 64. A lithographic inkcomposition according to claim 61, wherein the emulsified phase includesa weak acid.
 65. A lithographic ink composition according to claim 39,wherein the hydrogen bonding vinyl polymer has an equivalent weight,based on hydrogen bonding groups, of at least about 1800 grams perequivalent.
 66. A lithographic ink composition according to claim 39,wherein the hydrogen bonding vinyl polymer has an equivalent weight,based on hydrogen bonding groups, of up to about 20,000 grams perequivalent.
 67. A lithographic ink composition according to claim 39,wherein the hydrogen bonding vinyl polymer has an equivalent weight,based on hydrogen bonding groups, of from about 2200 grams perequivalent to about 7200 grams per equivalent.
 68. A lithographic inkcomposition according to claim 39, wherein the hydrogen bonding vinylpolymer is polymerized using at least one monomer having two or morepolymerizable ethylenically unsaturated bonds.
 69. A lithographic inkcomposition according to claim 39, wherein the hydrogen bonding vinylpolymer is polymerized using divinylbenzene.
 70. A lithographic inkcomposition according to claim 39, wherein the hydrogen bonding vinylpolymer is polymerized using at least about 0.008 equivalents per 100grams of monomer polymerized of at least one monomer having two or morepolymerizable ethylenically unsaturated bonds.
 71. A lithographic inkcomposition according to claim 39, wherein the hydrogen bonding vinylpolymer is polymerized using from about 0.012 to about 0.08 equivalentsper 100 grams of monomer polymerized of at least one monomer having twoor more polymerizable ethylenically unsaturated bonds.
 72. Alithographic ink composition according to claim 39, wherein the hydrogenbonding vinyl polymer is polymerized using from about 0.016 to about0.064 equivalents per 100 grams of monomer polymerized of at least onemonomer having two or more polymerizable ethylenically unsaturatedbonds.
 73. A lithographic ink composition according to claim 39, whereinthe hydrogen bonding vinyl polymer is polymerized using at least about0.004 equivalents per 100 grams of monomer polymerized of each of twomonomers having mutually reactive groups in addition to an ethylenicallyunsaturated polymerizable bond.
 74. A lithographic ink compositionaccording to claim 39, wherein the hydrogen bonding vinyl polymer hasbeen branched with a member selected from the group consisting ofaluminum gellants, alkoxylated titanates, alkoxylated zirconates, andcombinations thereof.
 75. A lithographic ink composition according toclaim 39, wherein the hydrogen bonding vinyl polymer has been branchedwith a member selected from the group consisting of aluminumacetoacetonate, aluminum triisopropoxide, aluminum tris-sec-butoxide,aluminum diisopropoxide aceto ester, aluminum oxyacylate, andcombinations thereof.
 76. A lithographic ink composition according toclaim 39, wherein the hydrogen bonding vinyl polymer has a numberaverage molecular weight of at least about 1000 and a weight averagemolecular weight of at least about 30,000.
 77. A lithographic inkcomposition according to claim 39, wherein the hydrogen bonding vinylpolymer has a weight average molecular weight of at least about 100,000.78. A lithographic ink composition according to claim 39, wherein thehydrogen bonding vinyl polymer has a polydispersity of at least about15.
 79. A lithographic ink composition according to claim 39, whereinthe hydrogen bonding vinyl polymer has a polydispersity of at leastabout
 50. 80. A lithographic ink composition according to claim 39,wherein the hydrogen bonding vinyl polymer has a polydispersity of fromabout 15 to about
 1000. 81. A lithographic ink composition according toclaim 39, wherein the hydrogen bonding vinyl polymer has apolydispersity of from about 50 to about
 800. 82. A lithographic inkcomposition according to claim 39, wherein the hydrogen bonding vinylpolymer has a theoretical glass transition temperature above roomtemperature.
 83. A lithographic ink composition according to claim 39,wherein the hydrogen bonding vinyl polymer has a theoretical glasstransition temperature of at least about 60° C.
 84. A lithographic inkcomposition according to claim 39, wherein the hydrogen bonding vinylpolymer has a theoretical glass transition temperature from about 50° C.to about 125° C.
 85. A lithographic ink composition according to claim39, wherein the continuous phase comprises a further material selectedfrom the group consisting of polyesters, alkyds, phenolics, rosins,cellulosics, rosin-modified phenolics, phenolic-modified rosins,hydrocarbon-modified rosins, maleic-modified rosins, fumaric-modifiedrosins, hydrocarbon resins, polyamides, vinyl polymers that do nothydrogen bond with the emulsified phase, and combinations thereof.
 86. Alithographic ink composition according to claim 85, wherein the furthermaterial is included in an amount of from about 1 part by weight up toabout 100 parts by weight for each part by weight of the hydrogenbonding vinyl polymer.
 87. A lithographic ink composition according toclaim 85, wherein the further material is included in an amount of fromabout 3 part by weight up to about 50 parts by weight for each part byweight of the hydrogen bonding vinyl polymer.
 88. A lithographic inkcomposition according to claim 39, wherein the hydrogen bonding vinylpolymer is polymerized using at least about 15% by weight of acrylicesters having at least six carbons in the alcohol portion, based ontotal monomer weight.
 89. A lithographic ink composition according toclaim 39, wherein the hydrogen bonding vinyl polymer is polymerizedusing from about 15% to about 30% by weight of acrylic esters havingfrom about eight to about twenty carbons in the alcohol portion, basedon total monomer weight.
 90. A lithographic ink composition according toclaim 39, wherein the hydrogen bonding vinyl polymer is polymerizedusing from about 50% to about 80% by weight of styrene, based on totalmonomer weight.
 91. A lithographic ink composition, comprising ahydrophobic, continuous phase comprising a solution of a branched,hydrogen bonding vinyl polymer and an emulsified phase having, asHansen's solubility parameter values, a dispersion parameter value of atleast about 6, a polarity parameter value of at least about 4, and ahydrogen bonding parameter value of at least about
 10. 92. Alithographic ink composition according to claim 91, wherein thedispersion parameter value is from about 8 to about 9, the polarityparameter value is from about 5 to about 8, and the hydrogen bondingparameter value is from about 12 to about
 20. 93. A lithographic inkcomposition, comprising a continuous phase comprising a vinyl polymercomprising primary amide groups, amide groups having N-alkylsubstituents of three or fewer carbon atoms, or combinations thereof,wherein the vinyl polymer has a polydispersity of at least about 15; andan emulsified phase comprising a member selected from the groupconsisting of water, liquid polyols, and combinations thereof.
 94. Alithographic ink composition according to claim 93, wherein theemulsified phase comprises a liquid polyol is selected from the groupconsisting of ethylene glycol, diethylene glycol, triethylene glycol,tetraethylene glycol, propylene glycol, 1,3-propanediol, dipropyleneglycol, and mixtures thereof.
 95. A lithographic ink compositionaccording to claim 93, wherein the ink composition includes from about5% to about 50% of the emulsified phase by weight.
 96. A lithographicink composition according to claim 93, wherein the ink compositionincludes from about 10% to about 35% of the emulsified phase by weight.97. A lithographic ink composition according to claim 93, wherein theink composition includes from about 20% to about 30% of the emulsifiedphase by weight.
 98. A lithographic ink composition according to claim93, wherein the emulsified phase includes a weak acid or a weak base.99. A lithographic ink composition according to claim 93, wherein theemulsified phase includes a member selected from the group consisting oflithium, sodium, potassium, magnesium, calcium, iron(II), manganese(II),copper(II), and zinc acetates, hydroxyacetates, nitrates, sulfates,phosphates, hydrogen phosphates, hydrogen sulfates, chlorates,chlorides, bromides, iodides, and combinations thereof.
 100. Alithographic ink composition according to claim 93, wherein theemulsified phase is nonaqueous.
 101. A lithographic ink compositionaccording to claim 93, wherein the vinyl polymer further comprises estergroups having pendant alkyl groups of three or fewer carbon atoms,β-hydroxyl ester groups, or combinations thereof.
 102. A lithographicink composition according to claim 101, wherein the vinyl polymer has anequivalent weight, based on total amide and ester groups, of from about2200 grams per equivalent to about 7200 grams per equivalent.
 103. Alithographic ink composition according to claim 102, wherein the amidegroups are obtained by copolymerizing N,N-dimethyl acrylamide and theester groups are obtained by copolymerizing methyl methacrylate.
 104. Alithographic ink composition according to claim 93, wherein the vinylpolymer has a number average molecular weight of between about 1000 andabout 15,000 and a weight average molecular weight of at least about100,000.
 105. A lithographic ink composition according to claim 93,wherein the continuous phase includes a further material selected fromthe group consisting of polyester resins, hydrocarbon resins, alkydresins, phenolic resins, rosins, cellulosic resins, and modificationsthereof, and mixtures thereof.
 106. A lithographic ink compositionaccording to claim 105, wherein the further material is less hydrophilicthan the acid-functional vinyl polymer.
 107. A method of making alithographic printing ink, comprising a step of combining a firstcomposition comprising an amide-functional, hydrogen bonding vinylpolymer and a second composition comprising a member selected from thegroup consisting of water, liquid polyols, and combinations thereof,whereby a printing ink is formed having as a continuous phase the firstcomposition and as a discontinuous phase the second composition.
 108. Alithographic ink composition according to claim 93, wherein theemulsified phase comprises water.
 109. A lithographic ink compositionaccording to claim 93, wherein the emulsified phase further comprises amember selected from the group consisting of solid polyol compounds,solid polyol oligomers, and compounds having one hydroxyl group and upto about 18 carbon atoms.
 110. A printing method, comprising a step ofprinting a substrate by lithographic printing using as a single fluidlithographic ink the ink according to claim
 1. 111. A printing method,comprising a step of printing a substrate by lithographic printing usingas a single fluid lithographic ink the ink according to claim 93.